Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups

Definitions

• This invention relates to polyamidopolyamines. More particularly, this invention relates to polyamidopolyamines prepared by reacting an aliphatic or an aromatic di-primary amine with the carboxy terminated reaction product of a poly(oxyethylene/oxypropylene) diamine or triamine with at least a bimolecular molar excess of an aromatic or aliphatic dicarboxylic acid, ester or anhydride thereof.
• this invention relates to novel polyamidopoly­amines prepared by reacting at least two mole equivalents of a polyoxypropylene, a polyoxyethylene or a poly(oxypropyl­ene/oxyethylene) diamine or triamine with an aromatic or aliphatic dicarboxylic acid to form a carboxy terminated intermediate product which is then reacted with an equimolar amount of an aliphatic or aromatic di-primary amine to thereby provide a polyamidopolyamine characterized by the presence of terminal primary amine groups and internal amido and carboxyl groups.
• the reactions are preferably conducted at autogenous pressure at temperatures within the range of about 150° to 250°C.
• the polyamidopolyamines of the present invention are liquids or amorphous solids, depending upon the starting materials, and can be used as raw materials for a wide variety of purposes such as, for example, as chain extenders for epoxy resins, curing agents for epoxy resins, as raw materials for the manufacture of polyureas, thickening agents, etc.
• the products may also be used as raw materials for the preparation of fuel and lubricant additives, for textile and fiber treating agents, for the preparation of adhesives, for use in the manufacture of polyureas, for use in encapsulation and molding applications, etc.
• polyoxyalkylene polyamines by the reductive amination of a polyoxyalkylene polyol.
• the reduc­tive amination is conducted catalytically in the presence of hydrogen and ammonia and an appropriate reductive amination catalyst, such as a nickel, copper and chromia catalyst.
• an appropriate reductive amination catalyst such as a nickel, copper and chromia catalyst.
• the polyoxyalkylene polyamines that are prepared in this fashion are stable articles of commerce having a wide vari­ety of uses such as those mentioned above. In particular, they have found utility as curing agents for epoxy resins, as plasticizers, as cross linking agents and binders for textiles, and as intermediates in the preparation of poly­ureas.
• polyoxyalkylene polyamines having mole­cular weights ranging from about 200 to about 5,000 can be prepared by the Yeakey process.
• Kwang U. S. Patent No. 3,257,342 is directed to epoxy resins that are cured with a polyamidodiamine prepared by reacting about two molar equivalents of a polyoxyalkylene­diamine with an aliphatic dicarboxylic acid.
• Klein U. S. Patent No. 4,133,803 is directed to the preparation of novel thermoplastic adhesive compositions having melting points between 20° and 180°C prepared by reacting a polyoxypropylene diamine or triamine with an aliphatic or aromatic dicarboxylic acid, ester or anhydride thereof.
• Klein used approximately equimolar amounts of carboxylic acid and polyamine. How­ever, he states that the molar ratio of the polyoxypropylene diamine or triamine to the dicarboxylic acid may range from about 0.25:1 to about 4.0:1.
• the thermoplastic adhesives of Klein are made by reacting the polyoxypropylene diamine or triamine with the dicarboxylic acid at about 175° to about 275°C for about 1 to 12 hours.
• thermoplastic adhesives The preparation of thermoplastic adhesives is disclosed in Schulze U. S. Patent No. 4,119,615.
• the adhesives are prepared by a two-step process. In the first step, about 1 to 4 moles of oxalic acid is reacted with a polyoxyalkylene diamine or triamine, the preferred ratio being a mole ratio of about 1 to 2 moles of oxalic acid per mole of polyoxy­alkylene diamine or triamine.
• This results in the formation of a so-called liquid prepolymer which is then reacted with an alkylene diamine such as ethylene diamine which contain 2 to 18 carbon atoms to provide the resinous polyoxyamide thermoplastic adhesive composition.
• Mains et al. U. S. Patent No. 4,062,819 is directed to polyamide polyblends wherein one component is a high molecu­lar weight thermoplastic polyamide and the other is a minor amount of a polyamide derived from a high molecular weight dibasic acid.
• the second component is prepared by reacting a dicarboxylic acid such as "dimer acids" with an aliphatic polyalkylene diamine such as ethylene diamine.
• Rasmussen U. S. Patent No. 4,218,351 discloses impact resistant thermoplastic polyamides which are suitable for use as hot melt adhesives and which contain, as a component, a minor amount of an amorphous amide-forming oligomer which is described as a polyoxyalkylene diamine having a number average molecular weight in the range of about 900 to about 5000.
• Rieder U. S. Patent No. 4,239,635 is directed to aque­ous metal working fluids containing a carboxylic acid group terminated polyoxyalkylene diamide or an alkali metal, ammonium or organic amine salt of the diamide.
• the diamide is prepared by reacting a dicarboxylic acid with a polyoxy­alkylenediamine in a 2:1 mole ratio.
• Chang U. S. Patent No. 4,588,783 relates to heat cura­ble compositions containing polyhydroxyethyl carbonates which are prepared by reacting an amidoamine with an organic carbonate.
• the amidoamines are prepared by reacting a poly­ester with an equivalent excess of a polyamine, for example, by reacting two moles of isophorone diamine with one mole of dimethylcyclohexane dicarboxylate.
• the polyoxyalkylene polyamines of the type disclosed in Yeakey U. S. Patent No. 3,654,370 are prepared by the oxy­alkylation of a polyhydric alcohol.
• the preferred starting materials are dihydric and trihydric alcohols such as propylene glycol or glycerol and propylene oxide or ethylene oxide.
• Copolymer polyols of ethylene oxide and propylene oxide are also useful, particularly those containing from about 5 to about 40 wt.% of ethylene oxide and, correspond­ingly, from about 95 to about 60 wt.% of propylene oxide.
• the molecular weight of the polyol is determined by the number of moles of epoxide that are reacted with the alcohol initiator. Since the addition is random, the final alkoxy­lation product will not be a pure compound but, rather, will be a mixture of polyoxyalkylene polyols.
• the polyol is a polyol prepared by reacting glycerol or trimethylol propane with propylene oxide, using an amount of propylene oxide adequate to provide for an average molecular weight of about 1,000, the final propoxylation product will actually be composed of a mixture of polyoxypropylene triols having molecular weights varying from about 800 to about 1,200, the molecular weight distribution following a Gaussian distribution curve (sometimes referred to as a sine curve or a Poissan curve). As the molecular weight of the polyol increases, the spread in the molecular weights will also increase. Thus, when the average molecular weight of the triol is about 3,000, the deviation will be about ⁇ 400 molecular weight units so that most of the product will fall within the molecular weight range of about 2,600 to about 3,400.
• a Gaussian distribution curve sometimes referred to as a sine curve or a Poissan curve
• the percentage of free hydroxyl groups in the reaction mixture will decrease because of the added bulk of the already formed polyol, thus making the addition of more propylene oxide groups progressively more difficult.
• the triol reaches an average molecular weight of about 5,000, further propoxylation is accomplished only with extreme difficulty.
• the 5,000 molecular weight poly­oxypropylene triols will have a molecular weight distribu­tion of about ⁇ 1,000 so that the actual molecular weight range will be from about 4,000 to about 6,000. Again, the molecular weight distribution following a Gaussian distribu­tion curve.
• a further complication is encountered during the pro­poxylation to the higher molecular weights.
• the reaction time and temperature are increased to encourage propoxyla­tion, there is introduced a tendency on the part of the propylene oxide to isomerize to allyl alcohol and a tendency on the part of the hydroxypropyl end groups of the polyoxy­propylene triol to dehydrate to form a terminal olefin group and water.
• Both the water and the allyl alcohol are suscep­tible to oxyalkylation thereby diluting the polyoxypropylene diol with undesired generally low molecular weight diol contaminants derived from the water and monofunctional allyl alcohol propoxylates. From as little as one percent to as much as ten percent of the oxypropyl end groups of the triol may dehydrate to form groups with terminal unsaturation in increasing the average molecular weight from about 3,000 to about 5,000.
• molecular weight distribution and terminal unsaturation problems such as those mentioned above are significantly reduced through the provision of aromatic amidoamines containing terminal primary amine groups which are analogous in function and reactivity to the polyoxyalkylene polyamines of Yeakey et al.
• Another significant property of the aromatic amidoamides of the present invention is the desirable increase in "stiffners” or "hardners” that is obtained without otherwise adversely affecting the other properties of the amidoamines.
• the resultant cured epoxy resin will frequently exhibit undesirable flex and impact properties and other related properties attrib­utable to the "rubbery" nature of the high molecular weight polyoxyalkylene polyamines.
• additives and/or fillers to provide a final cured epoxy resin having the desired physical properties.
• aromatic amidoamides of the present invention being significantly stiffer, can be used successfully with lesser quantities of fillers and/or additives or even without addi­tives.
• the addition of these amide groups adds phase mixing advantages (when used as epoxy curing agents) over conven­tional polyoxyalkylene polyamines in many situations.
• the improvements of the present invention are obtained through the provision of novel polyamidopolyamines which are prepared by the sequential reaction of an aliphatic or aromatic di-primary amine with a reaction product of at least a bimolecular excess of an aromatic or aliphatic dicarboxylic acid with a polyoxyethylene, a polyoxypropylene or a poly(oxyethylene/oxypropylene) diamine or triamine.
• the intermediate reaction products of the present invention are obtained by reacting a polyoxypropylene, a polyoxyethylene or a polyoxypropylene/polyoxyethylene di­amine or triamine with an aliphatic or aromatic dicarboxylic acid in molar proportions such that at least about 2 mole equivalents of carboxylic acid are provided in the reaction mixture for each mole equivalent of amine present in the reaction mixture.
• each of the primary amine groups of the polyamine will preferentially react with a carboxyl group of the carboxylic acid, ester or anhydride thereof and be linked thereto through an amide linkage to thereby provide a reaction product which is substantially free from terminal primary amine groups and is characterized by the presence of terminal carboxylic acid, anhydride or ester groups.
• the reaction between the polyoxyalkylene polyamine and the aromatic carboxylic acid, ester or anhydride thereof is preferably conducted in an autoclave at autogenous pressure which may suitably range from about 0 to about 1 atmospheres and at a temperature of from about 150° to about 250°C.
• autogenous pressure which may suitably range from about 0 to about 1 atmospheres and at a temperature of from about 150° to about 250°C.
• the reaction time required for completion of the reaction will normally range from about 0.5 to about 12 hours.
• By-product water of reaction is preferably removed as formed, so that the reaction product obtained at the end of the reaction is the desired final product.
• the thus-prepared intermediate reaction product is then reacted under essentially the same conditions outlined above with an aliphatic or aromatic di-primary amine to form the polyamidopolyamine reaction products of the present inven­tion which are characterized by the presence of terminal primary amine groups, the substantial absence of terminal carboxyl groups, and the presence of internal amido and carboxy groups.
• R represents an ethoxy, a propoxy or an ethoxy/­propoxy group having an average molecular weight of about 200 to about 7000
• R′ represents an aliphatic or an aromatic group having an average molecular weight of about 42 to about 1000 and containing from about 3 to about 70 carbon atoms
• R ⁇ represents an aliphatic or an aromatic group having an average molecular weight of about 24 to about 500 and containing from about 2 to about 35 carbon atoms
• x is a positive integer having a value of 2 or 3.
• reaction products of the present invention are essentially linear tetramido diprimary amines having the formula:
• R, R′ and R ⁇ have the meaning given above.
• reaction product when x is 3, the reaction product will be a hexamidohexacarboxytri-primary amine.
• R may also be defined as the nucleus of a polyoxyethyl­ene, polyoxypropylene of poly(oxyethylene/oxypropylene) diamine or triamine having the formula:
• R′′′ is the nucleus of an oxyalkylation susceptible dihydric or trihydric alcohol containing 2 to 6 carbon atoms; m is an integer having a value of 2 to 3; n is a number having an average value of about 1 to about 50; and R ⁇ ⁇ represents hydrogen or methyl.
• the dicarboxylic acid starting material for the present invention may be any suitable aliphatic or aromatic dicar­boxylic acid containing from about 3 to about 70 carbon atoms, having an average molecular weight of about 132 to about 1000 or an anhydride or a lower alkyl ester thereof wherein the alkyl group contains from about 1 to 4 carbon atoms and, more preferably, is methyl.
• Suitable aliphatic dicarboxylic acids include adipic acid, dodecanedioic acid, glu­taric acid, azelaic acid, sebacic acid, the so-called “dimer acid” prepared by the dimerization of unsaturated monocar­boxylic acids such as oleic acid, linoleic acid, eleostearic acid, and mixtures thereof which are sold commercially as "tall oil fatty acids”.
• dicarboxylic acids that may be used include brasslic acid, octadecanedioic acid, thapsic acid and dodecanedioic acid.
• aromatic dicarboxylic acid examples include acids such as terephthalic acid, isophthalic acid, trimesic acid, 1,1,3-trimethyl-3-phenylidan-4′,5-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, t-butyl isophthalic acid, etc. (i.e., benzene dicarboxylic acids and tricarboxylic acids, hemimellitic acid, trimellitic acid, 2-phenyl pen­tanedioic acid, etc.).
• acids such as terephthalic acid, isophthalic acid, trimesic acid, 1,1,3-trimethyl-3-phenylidan-4′,5-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, t-butyl isophthalic acid, etc.
• benzene dicarboxylic acids and tricarboxylic acids hemimellitic acid, trimellitic acid, 2-phenyl pen­
• the polyoxyalkylene polyamine starting materials for the present invention include polyoxypropylene diamines and triamines, polyoxyethylene diamines, and polyoxyalkylene diamines and triamines containing mixtures of both ethylene oxide and propylene oxide and, preferably, mixtures of from about 5 to about 40 wt.% of ethylene oxide with, correspond­ingly, from about 95 to 60 wt.% of propylene oxide.
• the ethylene oxide and propylene oxide may be premixed prior to reaction to form a hetero copolymer, or the ethylene oxide and the propylene oxide may be sequentially added to the ethoxylation kettle to form block oxypropylene/oxyethyl­ene copolymers.
• polyoxyalkylene polyamine starting material may be defined as a polyoxyalkylene polyamine hav­ing the formula:
• R is the nucleus of an oxyalkylation-­susceptible polyhydric alcohol containing 2 to 12 carbon atoms and 2 and 3 hydroxyl groups, and R′ is hydrogen or methyl, n is a number having an average value of 0 to 50, and m is an integer having a value of 2 to 3.
• the average molecular weight of the poly­oxypropylene diamine or triamine starting material will be from about 200 to about 5,000.
• polyoxyalkylene diamines that may be used are those that are sold by the Texaco Chemical Company as Jeffamine R D-series products having the formula:
• R′ independently represents hydrogen or methyl and x is a number having an average value of about 1 to about 60.
• Representative products having this structural formula include polyoxypropylene diols (wherein R′ is methyl) having an average molecular weight of about 230 wherein the value of x is between 2 and 3 (Jeffamine R D-230 amine), polyoxy­propylene diols having an average molecular weight of about 400 wherein x has a value between about 5 and 6 (Jeffamine R D-400 amine), and a polyoxypropylene diol product having an average molecular weight of about 2,000 wherein x has a value of about 33 (Jeffamine R D-2000 amine) and a product having an average molecular weight of about 4,000 wherein x has a value of about 60 (Jeffamine R D-4005 amine).
• polyoxyalkylene diamines containing both ethylene oxide and propylene oxide
• polyoxypropylene diamines sold by the Texaco Chemical Company as Jeffamine R ED-series products having the formula:
• a + c equals a number having a value of from about 2 to about 10 and b is a number having a value of from about 1 to about 50.
• Examples of products having this general formula include a commercial product having an average molecular weight of about 600 where the value of b is about 8.5 and the value of a + c is about 2.5 (Jeffamine R ED-600), a commercial product having an average molecular weight of about 900 wherein the value of a + c is again about 2.5, but the value of b is about 15.5 (Jeffamine R ED-900).
• a + c has a value of about 2.5 including a product having an average molecular weight of about 2,000 wherein the value of b is about 40 (Jeffamine R ED-2001) and a prod­uct having an average molecular weight of about 4,000 wherein the value of b is about 85 (Jeffamine R ED-4000).
• polyoxypropylene triamines that may be used as a starting material for the present invention include triamines sold by Texaco Chemical Company as Jeffamine R T-series products having the formula:
• A represents the nucleus of an oxyalkyla­tion susceptible trihydric alcohol containing about 3 to about 6 carbon atoms
• w, y and z are numbers and the average value of the sum of w + y + z is from about 4 to about 100.
• An example of such a product is a commercial product having an average molecular weight of about 400 wherein A represents a trimethylol propane nucleus, and the product contains about 5 to about 6 moles of propylene oxide (Jeffamine R T-403 amine) and a product having an average molecular weight of about 5,000 wherein A represents a glycerol nucleus and the product contains about 85 moles of propylene oxide (Jeffamine R T-5000).
• a dicarboxylic amidoamine reaction product is prepared by reacting the polyoxyalkylene polyamine starting material with at least 2 mole equivalents per mole of polyoxyalkylene polyamine starting material of an aliphatic or aromatic dicarboxylic acid of the type described above, or an ester or an anhy­dride thereof.
• the reaction is conducted noncatalytically at autogeneous pressure at a temperature within the range of about 150° to about 250°C. for a reaction time within the range of about 0.5 to about 12 hours. Normally, the reac­tion will go to completion after a reaction time within the range of about 2 to about 6 hours.
• By-product water of reaction is preferably removed from the reaction mixture as formed.
• the reaction is complete when essentially all of the amine groups of the polyoxy­alkylene polyamine have reacted with carboxyl groups of the dicarboxylic acid. Under the noncatalytic reaction condi­tions employed herein, the polyoxyalkylene diamine or triamine groups are essentially unreactive with each other.
• R, R′ and x have the meaning given above.
• the dicarboxyamidoamines that are formed in accordance with the present invention are liquid or amorphous solid materials having a molecular weight within the range of about 400 to about 15,000 and containing 2 or 3 terminal carboxylic acid, anhydride or ester groups.
• the interme­diate reaction product is reacted with a di-primary amine which may suitably be an aliphatic or an aromatic diamine.
• Such di-primary amines may be represented generally by the formula: (IX) H2N-R ⁇ -NH2
• R ⁇ has the meaning given above in formula (I).
• R ⁇ may suitably be an oxyethyl, a polyoxyethyl, an oxypropyl, a polyoxypropyl, a poly(ethoxy/propoxy), a phenyl, a substituted phenyl, an alkyl, a cycloalkyl, an ethylamino, a propylamino, etc., group.
• Representative aliphatic di-primary amines that may be used include compounds such as a polyoxyethylene diamine, a polyoxyethylene diamine containing from about 1 to about 5 oxyethylene groups, a polyoxypropylene diamine containing from about 1 to about 10 oxypropyl groups, isophorone di­amine, 1,2-diaminocyclohexane, 1,6-hexane diamine, ethylene­diamine, diethylene triamine, triethylene tetramine, tetra­ethylene pentamine, etc., propylene diamine, dipropylene triamine, tripropylene tetramine, etc.
• aromatic dicarboxylic acid and tricarboxylic acids that may be used as starting materials for the present invention include acids such as terephthalic acid, isophtha­lic acid, trimesic acid, 1,1,3-trimethyl-3-phenylidan-4′,5-­dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, t-butyl isophthalic acid, etc. (i.e., benzene dicarboxylic acids and tricarboxylic acids, hemimellitic acid, trimellitic acid, 2-phenyl pentanedioic acid, etc.).
• acids such as terephthalic acid, isophtha­lic acid, trimesic acid, 1,1,3-trimethyl-3-phenylidan-4′,5-­dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, t-butyl isophthalic acid, etc.
• an intermedi­ate reaction product of the type described above is reacted with a di-primary amine to form a reaction addition product comprising the polyamidodi- or tri-primary amine reaction products of the present invention as represented by the following formula:
• R represents an ethoxy, a propoxy or an ethoxy/­propoxy group having an average molecular weight of about 200 to about 7000
• R′ represents an aliphatic or an aromatic group having an average molecular weight of about 42 to about 1000 and containing from about 3 to about 70 carbon atoms
• R ⁇ represents an aliphatic or an aromatic group having an average molecular weight of about 24 to about 500 and containing from about 2 to about 36 carbon atoms
• x is a positive integer having a value of 2 or 3.
• the polyamidodi- and tri-primary amines are prepared by reacting the intermediate reaction product with an equimolar amount of the di-primary amine reactant described above at autogenous pressure at a temperature within the range of about 150° to about 250°C. for a reaction time within the range of about 0.5 to 12 hours. Normally, the reaction will go to completion after a reaction time within the range of about 2 to about 6 hours.
• By-product water reaction is preferably removed from the reaction mixture as formed.
• the reaction is complete when essentially all of the carboxyl groups have reacted with the primary amine groups of the di-primary amine.
• the polyamidopolydi-primary or tri-primary amines pre­pared in the above described manner are liquid or amorphous solid materials having a molecular weight within the range of about 600 to about 15,000 and contain an average of about 2 to about 3 terminal primary amine groups, depending on the functionality of the polyoxyalkylenepolyamine starting material.
• the product was soluble in methanol, but insoluble in water or acetone.
• the amine analysis indicated 0.39 meq/g (theoretical 0.40 meq/g) and acidity was 0.02 meq/g.
• the IR spectrum showed the evidence of amide formation.
• the example illustrates a two-step, one-pot synthesis of an amidoamine with an EDR-series amine as the terminal amine.
• a soap dish was made by mixing amine (prepared from JEFFAMINE R D-2000-adipic acid-DETDA, 6153-27), 32.7g, dipropyltriamine, 6.6g, and Epon 828 (from Shell) 56.1g.
• the well mixed material was poured into a plastic mold and cured at 70°C. for overnight. The experiment demonstrated the usage of one amine in epoxy resin material application.
• D-400-adipic acid adduct prepared from 6152-83, 65.6g, 0.1M
• 1,6-hexanediamine (23.2g, 0.2M)
• the mixture was then heated to 204°C. to remove water.
• the reaction was run for ca. 4 hour period of time and then cooled to room temperature.
• a solid material form of product was recovered.
• the analysis showed 2.51 meq/g amine (calc. 2.2 meq/g).
• the resulting product from 6153-50 was a viscous light yellow liquid and methanol soluble.
• This product (69.4g) was mixed with Epon 828 (Shell; 18.7g) and cured at 78°C. overnight.
• Epon 828 Shell; 18.7g
• a flexible, transparent, yellowish epoxy resin was made. The experiment demonstrated the usage of one amine in epoxy resin material applications.
• T-5000-adipic acid adduct by mixing JEFFAMINE T-5000, 289g and adipic acid 21.9g.
• the two reactants were heated at 200-220°C. to remove water) and diethyltoluene diamine (53.4g).
• the contents were further heated at 220 C. for 3 hours and then cooled to room temperature.
• Analyses of the viscous brown liquid (350g) indicated 1.58 meq/g amine and 0.34 meq/g acidity.
• Example 9 Using the same procedure of Example 9, a product of T-2000-dimer acid-DETDA (1:3:3 molar ratio adduct) was prepared, with analyses of 1.19 meq/g amine and 0.40 meq/g acid. A portion of product 6199-1 (4.2g) was mixed thoroughly with Epon 828 (Shell product, 18.7g), then poured to a mole and cured at 78°C. overnight. A flexible epoxy resin material was made.
• D-400-adipic acid adduct (6152-83, 65.6g) and dipropyltri­amine (26.2g).
• the mixture was heated to 170-220°C. for over 4 hours and 3.6 cc of water removed.
• the recovered product was analyzed to be 0.01 meq/g for acidity, 2.06 meq/g for primary amine and 2.11 meq/g for secondary amine.
• Plastic Part I Plastic Part I .
• Product 6152-31, 67.5g (0.05 meq) was mixed with 9.3g of Epon 828 (0.05 meq, diglycidol ether of bisphenol-A, Shell chemical Co.).
• Epon 828 0.05 meq, diglycidol ether of bisphenol-A, Shell chemical Co.
• the viscous material was poured into a flexible urethane mold to form a soap dish.
• the mold was placed in an oven and held overnight at 70°C.
• a rubbery epoxy part was obtained which was rather tough and elasic even though a deficiency of amine was present.
• Plastic Part III To add toughness to the elastic epoxies obtained as described above, we added a higher crosslinking amine. To the mold was added 33.8g of 6152-31, 56.1g of Epon 828 and 6.6g of dipropylenetriamine. The mixture and mold were heated in an oven at 63°C. overnight. We obtained autogenous phase separation. The shell of the turtle was very hard while the bottom was made of the flexible epoxy. Such one-pour, two-phase objects should have many applications for hard objects requiring a soft support, objects of art, floors, and building supports in earthquake areas.

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